A degradable MOF amino resin film

Abstract

The present invention belongs to the field of degradable polymer membranes. The present invention relates to a degradable MOF amino resin membrane and a preparation method thereof. The method mainly uses MOF materials to modify amino resins, and blends them with PVA and starch to prepare a degradable amino resin membrane material. The degradable MOF amino resin membrane can not only effectively solve the "white pollution" of agricultural films in the prior art and the defect of damaging soil fertility, but on the contrary, the organic raw materials formed after degradation contain abundant elements such as C, O, N, P, S, Fe (or Zn), K, etc., which are necessary for the growth of crops, and can effectively enhance the soil fertility; and can also improve the high CO2 concentration environment required for crop growth.

Description

Technical Field

[0001] The present invention relates to a degradable MOF amino resin film and a preparation method thereof. The present invention belongs to the field of degradable polymer films. Background Art

[0002] The film mulching technology is an important revolution in agricultural production. It can adjust the soil temperature, reduce the loss of fertilizer efficiency, and has the functions of flood resistance and drought prevention. It is widely used in the cultivation of crops and is an important measure to improve product quality and yield. At present, agricultural plastic films are mainly made of polyethylene and polyvinyl chloride, which have a slow degradation rate and require hundreds of years to completely degrade, resulting in white pollution. At the same time, the degradation of plastics will release phthalic acid esters, which are carcinogenic substances. When released into the soil, they will pollute the environment. In addition, the residual plastic film mulch in the soil will also reduce the number of soil microorganisms and the activity of enzymes, leading to soil compaction and loss of fertilizer efficiency.

[0003] In recent years, with the promotion of plastic removal and plastic bans, developing biodegradable plastic films to replace traditional plastic films is the fundamental way to solve white pollution. Polyvinyl alcohol (PVA) and starch, as biodegradable materials, are environmentally friendly organic polymer polymers with good film-forming properties and biocompatibility, and have broad application prospects in the field of film materials such as food packaging and biomedicine. The larger the molecular weight of the PVA material, the greater the density, the more the intermolecular entanglement and cross-linking, and the higher the degree of polymerization, the smaller its solubility and viscosity. However, pure PVA materials have disadvantages such as high cost and slow degradation rate in the soil. Adding starch to PVA materials can improve the biodegradation rate of the materials and produce more economical and environmentally friendly starch / PVA-based materials. Due to the limited compatibility between starch and PVA, the mechanical properties, thermal stability, hydrophobicity, water resistance, etc. of PVA / starch blend materials are poor, which severely restricts the application of PVA / starch composite materials.

[0004] When amino resin (urea formaldehyde resin) is used to produce plastic films, the plastic film covers the soil surface and has certain water resistance and anti-ultraviolet aging properties. When the plastic film is no longer needed, it only needs to be buried under the soil and can be completely degraded within a few months; no harmful substances are produced during the degradation process, which is green and pollution-free; and during the degradation process, nitrogen fertilizer and trace amounts of phosphorus and potassium fertilizers are slowly released, continuously providing fertilizer efficiency for the soil. However, due to its high cross-linking density, the internal stress of amino resin is too large, resulting in poor film-forming properties.

[0005] Metal-organic frameworks (MOFs) are organic-inorganic hybrid materials formed by the self-assembly of organic ligands and metal ions or clusters through coordination bonds, and have potential applications in the fields of polymer composites, gas adsorption and separation, etc.

[0006] In view of the above factors, it has certain production and application value to modify amino resin with MOF materials and blend-modify it with PVA and starch to prepare a degradable amino resin film. Summary of the Invention

[0007] The object of the present invention is to provide a preparation method of a degradable MOF amino resin film in view of the "white pollution" of agricultural mulch films and the defect of damaging soil fertility in the prior art. It uses self-made MOF-modified urea-formaldehyde resin and is prepared by blending and modifying it with PVA resin and starch. While solving the problem of degradation of polymer films, the organic raw materials formed after degradation contain rich elements such as C, O, N, P, S, Fe (or Zn), K, etc. that are necessary for crop growth, which can effectively enhance the soil fertility; and at the same time, it can also create a high CO2 concentration environment required for crop growth.

[0008] The technical solution adopted by the present invention to solve its technical problems is as follows:

[0009] A degradable MOF amino resin film, comprising the following raw materials in parts by weight:

[0010] 40-70 parts of MOF-modified amino resin;

[0011] 20-35 parts of PVA resin;

[0012] 5-30 parts of starch.

[0013] Preferably, the MOF-modified amino resin is prepared by the following method:

[0014] Add formaldehyde solution, add potassium hydroxide, adjust the pH to 4.5-5.5, then add urea A, melamine, heat up to 85-90 °C and react for 1-1.5 h; add acid to make the pH of the reaction solution 4.0-5.0, control the temperature at 80-90 °C, keep warm until the viscosity reaches 100-150 cps, add MOF material, continue stirring for 0.5-1 h, then add urea B, adjust the pH of the reaction solution to 6.5-7.5 with potassium hydroxide, and stop the reaction to obtain MOF-modified amino resin;

[0015] The dosage ratio of the formaldehyde solution, urea A, melamine, MOF material, and urea B is 100 g: 24-30 g: 5 g: 5-20 g: 25-31 g;

[0016] The formaldehyde solution is 37 wt% aqueous formaldehyde solution.

[0017] Preferably, the acid is ammonium sulfate.

[0018] Preferably, the MOF material is an iron-based MOF material or a zinc-based MOF material.

[0019] Preferably, the iron-based MOF material is prepared by the following method:

[0020] The iron salt, phosphoric acid, oxalic acid, and urea are dissolved in deionized water A. After stirring well, it is transferred to a reaction kettle. After the reaction kettle is completely sealed, it is placed in an oven at 100-110°C for reaction for 24-30 h; after the reaction is completed, it is cooled to room temperature, and the obtained product is washed 3 times with deionized water B and dried at 60°C for 24 h to obtain the iron-based MOF material;

[0021] The molar ratio of the iron salt, phosphoric acid, oxalic acid, urea, and deionized water A is 1:4:3:3:80.

[0022] Preferably, the iron salt is ferric chloride hexahydrate or ferric nitrate nonahydrate.

[0023] Preferably, the zinc-based MOF material is prepared by the following method:

[0024] The zinc salt, phosphoric acid, oxalic acid, and urea are dissolved in N,N-dimethylformamide A. It is continuously magnetically stirred at a speed of 300 r / min at room temperature for 15 min until completely dissolved; then it is transferred to a reaction kettle. After the reaction kettle is completely sealed, it is placed in an oven at 120°C for reaction for 24 h; after the reaction is completed, it is naturally cooled to room temperature, and the obtained product is washed 3 times with N,N-dimethylformamide B and dried at 60°C for 24 h to obtain the zinc-based MOF material;

[0025] The molar ratio of the zinc salt, phosphoric acid, oxalic acid, urea, and N,N-dimethylformamide A is 1:4:2:3:80.

[0026] Preferably, the zinc salt is zinc nitrate hexahydrate or zinc acetate.

[0027] A preparation method of a degradable MOF amino resin film includes the following steps:

[0028] (1) An acidic curing agent is added to the MOF-modified amino resin and stirred and mixed evenly to obtain an amino resin glue solution for standby;

[0029] The dosage ratio of the MOF-modified amino resin to the acidic curing agent is 100 g: 3-5 g;

[0030] (2) The PVA resin is added to deionized water C and stirred and dissolved at 50°C to obtain a PVA solution for standby; the starch is added to deionized water D and stirred at room temperature for 5 min to obtain a uniform starch dispersion for standby;

[0031] The dosage ratio of the PVA resin to deionized water C is 10 g: 80 g;

[0032] The dosage ratio of the starch to deionized water D is 10 g: 50 g;

[0033] (3) Add the obtained starch dispersion into the PVA solution, and stir at 80 °C for 60 min to obtain a uniform PVA / starch blend solution for standby.

[0034] (4) Add the PVA / starch blend solution obtained in step (3) into the amino resin sizing agent obtained in step (1), and stir and mix at 80 °C for 60 min to obtain a uniform film-forming solution for standby.

[0035] (5) Pour the film-forming solution obtained in step (4) into a flat glass dish, and dry it in an oven at 60 - 80 °C for 8 - 12 h to obtain the degradable MOF amino resin film.

[0036] Preferably, the acidic curing agent is ammonium sulfate or metaphosphoric acid.

[0037] Advantages of the present invention:

[0038] (1) The present invention provides a degradable MOF amino resin film, which is mainly composed of MOF material-modified amino resin. First, the MOF material contains abundant P, N, Fe (or Zn) elements, which can improve the soil fertility; second, the MOF material is molecularly designed with urea as the structure-directing agent to modify the amino structure, improving the dispersion of the MOF material in the amino resin; third, the MOF material has a high-porosity structure and is modified with ester groups and polar amino groups, having a high capture rate for carbon dioxide and can improve the photosynthesis efficiency of crops; fourth, using oxalic acid as the organic ligand, the MOF material in the soil can be degraded by the oxalic acid-carbonic acid pathway mediated by microorganisms, accelerating the mineralization and nutrient release of the MOF; fifth, the multi-polar structure of the MOF material can improve the compatibility between the amino resin, PVA resin and starch, improving the mechanical properties.

[0039] (2) The present invention provides a degradable MOF amino resin film, which is mainly composed of MOF material-modified amino resin. First, the amino resin mainly composed of urea has degradable characteristics; and after degradation, it provides the nitrogen fertilizer required for crops; second, the pH regulators used in the process of preparing the amino resin are potassium hydroxide and ammonium sulfate, providing the K and S elements required for the growth of crops and improving the fertilizer efficiency; third, the degradation process is a slow process, which provides a slow-release function for the fertilizer efficiency of the amino resin.

[0040] (3) The present invention provides a degradable MOF amino resin film containing PVA resin and starch. First, PVA and starch are completely biodegradable materials; second, the internal stress of the amino resin is relatively large, and its flexibility can be improved after blending with PVA and starch, facilitating film formation; third, blending and compounding PVA / starch with MOF material-modified amino resin to form a film can effectively improve the gas barrier property of the PVA / starch composite film, increase the degradation rate, and promote the growth of crops.

[0041] (4) The present invention provides a preparation method of a degradable MOF amino resin film. Through molecular design, it has the advantage of complete degradability. The degradation process is a slow-release process of fertilizer efficiency, with rich elements required for crop growth and excellent gas selective permeability. Detailed implementation mode

[0042] The present invention will be described in detail below in conjunction with embodiments. However, it should be understood that the following embodiments are only illustrative examples of the implementation modes of the present invention, rather than limiting the scope of the present invention.

[0043] In the following embodiments of the present invention, the dosage of the MOF-modified amino resin is in parts by solid weight.

[0044] In the following embodiments of the present invention, the PVA resin: PVA-117 type, with a weight average molecular weight of 14.5 KDa, is purchased from Aladdin Biochemical Company.

[0045] In the following embodiments of the present invention, the starch is purchased from Sinopharm Chemical Reagent Co., Ltd.

[0046] Example 1

[0047] A degradable MOF amino resin film contains the following raw materials in parts by weight:

[0048] 60 parts of MOF-modified amino resin;

[0049] 30 parts of PVA resin;

[0050] 10 parts of starch.

[0051] The above MOF-modified amino resin is prepared by the following method:

[0052] Add an aqueous formaldehyde solution of 37 wt% and potassium hydroxide, adjust the pH to 5, then add urea A and melamine, heat up to 85 °C and react for 1.5 h; add ammonium sulfate to make the pH of the reaction solution 4.5, control the temperature at 85 °C, keep warm until the viscosity reaches 136 cps, add the iron-based MOF material, continue stirring for 0.8 h, then add urea B, adjust the pH of the reaction solution to 7 with potassium hydroxide, and stop the reaction to obtain the MOF-modified amino resin;

[0053] The dosage ratio of the 37 wt% aqueous formaldehyde solution, urea A, melamine, iron-based MOF material, and urea B is 100 g: 27 g: 5 g: 10 g: 29 g.

[0054] Its infrared data is as follows: 3366 cm -1 : There is a broad peak of active hydrogen (-OH, -NH-); 1658 cm -1 : -C=O exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 606 cm -1 、432 cm -1 : Fe-O exists; 676 cm -1 : Fe-N exists; 1557 cm -1 、1360 cm -1 、812 cm -1 : The triazine ring exists; 1720 cm -1 : The aldehyde group -C=O does not exist.

[0055] The above iron-based MOF material is prepared by the following method:

[0056] Ferric chloride hexahydrate, phosphoric acid, oxalic acid, and urea are dissolved in deionized water A, stirred evenly, transferred to a reaction kettle, sealed completely, and placed in an oven at 110 °C for 24 h; after the reaction, it is cooled to room temperature, and the obtained product is washed 3 times with deionized water B and dried at 60 °C for 24 h to obtain the iron-based MOF material;

[0057] The molar ratio of the ferric chloride hexahydrate, phosphoric acid, oxalic acid, urea, and deionized water A is 1: 4: 3: 3: 80.

[0058] Its infrared data is as follows: 3328 cm -1 : There is a broad peak of active hydrogen (-OH, -NH-); 1654 cm -1 : -C=O exists; 1431 cm -1 : -C-C- exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 606 cm -1 、432 cm -1 : Fe-O exists; 676 cm -1 : Fe-N exists.

[0059] A preparation method of a degradable MOF amino resin film includes the following steps:

[0060] (1) Ammonium sulfate is added to the MOF-modified amino resin, stirred and mixed evenly to obtain an amino resin sizing solution for standby;

[0061] The dosage ratio of the MOF-modified amino resin to ammonium sulfate is 100 g: 5 g;

[0062] (2) Add the PVA resin to deionized water C, stir and dissolve it at 50 °C to obtain a PVA solution for standby; add starch to deionized water D, stir at room temperature for 5 min to obtain a uniform starch dispersion for standby;

[0063] The dosage ratio of the PVA resin to deionized water C is 10 g: 80 g;

[0064] The dosage ratio of the starch to deionized water D is 10 g: 50 g;

[0065] (3) Add the obtained starch dispersion to the PVA solution, stir at 80 °C for 60 min to obtain a uniform PVA / starch blend solution for standby;

[0066] (4) Add the PVA / starch blend solution obtained in step (3) to the amino resin sizing agent obtained in step (1), stir and mix at 80 °C for 60 min to obtain a uniform film-forming liquid for standby;

[0067] (5) Pour the film-forming liquid obtained in step (4) into a flat-bottomed glass dish, and dry it in an oven at 80 °C for 8 h to obtain the degradable MOF amino resin film.

[0068] Example 2

[0069] A degradable MOF amino resin film, comprising the following raw materials in parts by weight:

[0070] 70 parts of MOF-modified amino resin;

[0071] 20 parts of PVA resin;

[0072] 10 parts of starch.

[0073] The above MOF-modified amino resin is prepared by the following method:

[0074] Add 37 wt% aqueous formaldehyde solution, add potassium hydroxide, adjust the pH to 5.5, then add urea A, melamine, heat up to 90 °C and react for 1.5 h; add ammonium sulfate to make the pH of the reaction solution 5.0, control the temperature at 90 °C, keep warm until the viscosity reaches 150 cps, add iron-based MOF material, continue stirring for 1 h, then add urea B, adjust the pH of the reaction solution to 6.5 with potassium hydroxide, and stop the reaction to obtain the MOF-modified amino resin;

[0075] The dosage ratio of the 37 wt% aqueous formaldehyde solution, urea A, melamine, iron-based MOF material, and urea B is 100 g: 30 g: 5 g: 5 g: 31 g.

[0076] Its infrared data is as follows: 3366 cm -1 : The broad peak of active hydrogen (-OH, -NH-) exists; 1658 cm -1 : -C=O exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 606 cm -1 and 432 cm -1 : Fe-O exists; 676 cm -1 : Fe-N exists; 1557 cm -1 and 1360 cm -1 and 812 cm -1 : Triazine ring exists; 1720 cm -1 : Aldehyde group -C=O does not exist.

[0077] The above iron-based MOF material is prepared by the following method:

[0078] Ferric nitrate nonahydrate, phosphoric acid, oxalic acid, and urea are dissolved in deionized water A. After stirring evenly, it is transferred to a reaction kettle. After the reaction kettle is completely sealed, it is placed in an oven at 100 °C for 30 h; after the reaction, it is cooled to room temperature. The obtained product is washed 3 times with deionized water B and dried at 60 °C for 24 h to obtain the iron-based MOF material;

[0079] The molar ratio of ferric nitrate nonahydrate, phosphoric acid, oxalic acid, urea, and deionized water A is 1:4:3:3:80.

[0080] Its infrared data is as follows: 3328 cm -1 : The broad peak of active hydrogen (-OH, -NH-) exists; 1654 cm -1 : -C=O exists; 1431 cm -1 : -C-C- exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 606 cm -1 and 432 cm -1 : Fe-O exists; 676 cm -1 : Fe-N exists.

[0081] A preparation method of a degradable MOF amino resin film includes the following steps:

[0082] (1) Ammonium sulfate is added to the MOF-modified amino resin and stirred evenly to obtain an amino resin sizing solution for standby;

[0083] The dosage ratio of the MOF-modified amino resin to ammonium sulfate is 100 g:5 g;

[0084] (2) Add the PVA resin to deionized water C, stir and dissolve it at 50 °C to obtain a PVA solution for standby; add the starch to deionized water D, stir at room temperature for 5 min to obtain a uniform starch dispersion for standby;

[0085] The dosage ratio of the PVA resin to deionized water C is 10 g: 80 g;

[0086] The dosage ratio of the starch to deionized water D is 10 g: 50 g;

[0087] (3) Add the obtained starch dispersion to the PVA solution, stir at 80 °C for 60 min to obtain a uniform PVA / starch blend solution for standby;

[0088] (4) Add the PVA / starch blend solution obtained in step (3) to the amino resin sizing agent obtained in step (1), stir and mix at 80 °C for 60 min to obtain a uniform film-forming solution for standby;

[0089] (5) Pour the film-forming solution obtained in step (4) into a flat-bottomed glass dish, dry it in an oven at 60 °C for 12 h to obtain the degradable MOF amino resin film.

[0090] Example 3

[0091] A degradable MOF amino resin film, comprising the following raw materials in parts by weight:

[0092] 40 parts of MOF-modified amino resin;

[0093] 30 parts of PVA resin;

[0094] 30 parts of starch.

[0095] The above MOF-modified amino resin is prepared by the following method:

[0096] Add 37 wt% aqueous formaldehyde solution, add potassium hydroxide, adjust the pH to 4.5, then add urea A, melamine, heat up to 85 °C and react for 1 h; add ammonium sulfate to make the pH of the reaction solution 4.0, control the temperature at 80 °C, keep warm until the viscosity reaches 100 cps, add the iron-based MOF material, continue to stir for 0.5 h, then add urea B, adjust the pH of the reaction solution to 7.5 with potassium hydroxide, and stop the reaction to obtain the MOF-modified amino resin;

[0097] The dosage ratio of the 37 wt% aqueous formaldehyde solution, urea A, melamine, iron-based MOF material, and urea B is 100 g: 24 g: 5 g: 20 g: 25 g.

[0098] Its infrared data is as follows: 3366 cm -1: There is a broad peak of active hydrogen (-OH, -NH-); 1658 cm -1 : -C=O exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 606 cm -1 、432 cm -1 : Fe-O exists; 676 cm -1 : Fe-N exists; 1557 cm -1 、1360 cm -1 、812 cm -1 : Triazine ring exists; 1720 cm -1 : Aldehyde group -C=O does not exist.

[0099] The above iron-based MOF material is prepared by the following method:

[0100] Ferric chloride hexahydrate, phosphoric acid, oxalic acid, and urea are dissolved in deionized water A. After stirring evenly, it is transferred to a reaction kettle. After the reaction kettle is completely sealed, it is placed in an oven at 110 °C for reaction for 28 h; after the reaction, it is cooled to room temperature, and the obtained product is washed 3 times with deionized water B and dried at 60 °C for 24 h to obtain the iron-based MOF material;

[0101] The molar ratio of the ferric chloride hexahydrate, phosphoric acid, oxalic acid, urea, and deionized water A is 1:4:3:3:80.

[0102] Its infrared data are as follows: 3328 cm -1 : There is a broad peak of active hydrogen (-OH, -NH-); 1654 cm -1 : -C=O exists; 1431 cm -1 : -C-C- exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 606 cm -1 、432 cm -1 : Fe-O exists; 676 cm -1 : Fe-N exists.

[0103] A preparation method of a degradable MOF amino resin film includes the following steps:

[0104] (1) Ammonium sulfate is added to the MOF-modified amino resin and stirred and mixed evenly to obtain an amino resin glue solution for standby;

[0105] The dosage ratio of the MOF-modified amino resin to ammonium sulfate is 100 g: 4 g;

[0106] (2) Add the PVA resin to deionized water C and stir to dissolve it at 50 °C to obtain a PVA solution for standby. Add the starch to deionized water D and stir for 5 min at room temperature to obtain a uniform starch dispersion for standby.

[0107] The dosage ratio of the PVA resin to deionized water C is 10 g:80 g.

[0108] The dosage ratio of the starch to deionized water D is 10 g:50 g.

[0109] (3) Add the obtained starch dispersion to the PVA solution and stir for 60 min at 80 °C to obtain a uniform PVA / starch blend solution for standby.

[0110] (4) Add the PVA / starch blend solution obtained in step (3) to the amino resin sizing agent obtained in step (1) and stir and mix for 60 min at 80 °C to obtain a uniform film-forming liquid for standby.

[0111] (5) Pour the film-forming liquid obtained in step (4) into a flat-bottomed glass dish and dry it in an oven at 70 °C for 10 h to obtain the degradable MOF amino resin film.

[0112] Example 4

[0113] A degradable MOF amino resin film, comprising the following raw materials in parts by weight:

[0114] 50 parts of MOF-modified amino resin;

[0115] 30 parts of PVA resin;

[0116] 20 parts of starch.

[0117] The above-mentioned MOF-modified amino resin is prepared by the following method:

[0118] Add 37 wt% aqueous formaldehyde solution, add potassium hydroxide, adjust the pH to 5, then add urea A, melamine, and raise the temperature to 85 °C and react for 1 h. Add ammonium sulfate to make the pH of the reaction solution 4.5, control the temperature at 90 °C, keep warm until the viscosity reaches 120 cps, add the iron-based MOF material, continue to stir for 0.8 h, then add urea B, and adjust the pH of the reaction solution to 7 with potassium hydroxide to stop the reaction, thus obtaining the MOF-modified amino resin.

[0119] The dosage ratio of the 37 wt% aqueous formaldehyde solution, urea A, melamine, iron-based MOF material, and urea B is 100 g:25 g:5 g:15 g:27 g.

[0120] Its infrared data is as follows: 3366 cm -1 : The broad peak of active hydrogen (-OH, -NH-) exists; 1658 cm-1 : -C=O exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 606 cm -1 and 432 cm -1 : Fe-O exists; 676 cm -1 : Fe-N exists; 1557 cm -1 and 1360 cm -1 and 812 cm -1 : Triazine ring exists; 1720 cm -1 : Aldehyde group -C=O does not exist.

[0121] The above iron-based MOF material is prepared by the following method:

[0122] Iron(III) nitrate nonahydrate, phosphoric acid, oxalic acid, and urea are dissolved in deionized water A. After stirring well, it is transferred to a reaction kettle. The reaction kettle is sealed completely and placed in an oven at 100 °C for reaction for 30 h; after the reaction is completed, it is cooled to room temperature. The obtained product is washed 3 times with deionized water B and dried at 60 °C for 24 h to obtain the iron-based MOF material;

[0123] The molar ratio of the iron(III) nitrate nonahydrate, phosphoric acid, oxalic acid, urea, and deionized water A is 1:4:3:3:80.

[0124] Its infrared data are as follows: 3328 cm -1 : Broad peak of active hydrogen (-OH, -NH-) exists; 1654 cm -1 : -C=O exists; 1431 cm -1 : -C-C- exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 606 cm -1 and 432 cm -1 : Fe-O exists; 676 cm -1 : Fe-N exists.

[0125] A preparation method of a degradable MOF amino resin film includes the following steps:

[0126] (1) Ammonium sulfate is added to the MOF-modified amino resin and stirred and mixed evenly to obtain an amino resin sizing solution for standby;

[0127] The dosage ratio of the MOF-modified amino resin to ammonium sulfate is 100 g: 4.5 g;

[0128] (2) Add the PVA resin to deionized water C, stir and dissolve it at 50 °C to obtain a PVA solution for standby; add starch to deionized water D, stir at room temperature for 5 min to obtain a uniform starch dispersion for standby;

[0129] The dosage ratio of the PVA resin to deionized water C is 10 g:80 g;

[0130] The dosage ratio of the starch to deionized water D is 10 g:50 g;

[0131] (3) Add the obtained starch dispersion to the PVA solution, stir at 80 °C for 60 min to obtain a uniform PVA / starch blend solution for standby;

[0132] (4) Add the PVA / starch blend solution obtained in step (3) to the amino resin sizing agent obtained in step (1), stir and mix at 80 °C for 60 min to obtain a uniform film-forming solution for standby;

[0133] (5) Pour the film-forming solution obtained in step (4) into a flat-bottomed glass dish, and dry it in an oven at 80 °C for 8 h to obtain a degradable MOF amino resin film.

[0134] Example 5

[0135] A degradable MOF amino resin film, comprising the following raw materials in parts by weight:

[0136] 60 parts of MOF-modified amino resin;

[0137] 30 parts of PVA resin;

[0138] 10 parts of starch.

[0139] The above MOF-modified amino resin is prepared by the following method:

[0140] Add an aqueous formaldehyde solution of 37 wt%, add potassium hydroxide, adjust the pH to 5, then add urea A, melamine, and raise the temperature to 85 °C and react for 1.5 h; add ammonium sulfate to make the pH of the reaction solution 4.5, control the temperature at 85 °C, keep warm until the viscosity reaches 135 cps, add the zinc-based MOF material, continue stirring for 0.8 h, then add urea B, adjust the pH of the reaction solution to 7 with potassium hydroxide, and stop the reaction to obtain the MOF-modified amino resin;

[0141] The dosage ratio of the 37 wt% aqueous formaldehyde solution, urea A, melamine, MOF material, and urea B is 100 g:27 g:5 g:10 g:29 g.

[0142] Its infrared data is as follows: 3366 cm -1 : The broad peak of active hydrogen (-OH, -NH-) exists; 1658 cm-1 : -C=O exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 381 cm -1 : Zn-O exists; 449 cm -1 : Zn-N exists; 1720 cm -1 : 1557 cm -1 、1360 cm -1 、812 cm -1 : Triazine ring exists; aldehyde group -C=O does not exist.

[0143] The above zinc-based MOF material is prepared by the following method:

[0144] Zinc nitrate hexahydrate, phosphoric acid, oxalic acid, and urea are dissolved in N,N-dimethylformamide A, and magnetically stirred continuously at a speed of 300 r / min at room temperature for 15 min until completely dissolved; then transferred to a reaction kettle. After the reaction kettle is completely sealed, it is placed in an oven at 120 °C for 24 h; after the reaction is completed, it is naturally cooled to room temperature, and the obtained product is washed 3 times with N,N-dimethylformamide B and dried at 60 °C for 24 h to obtain the zinc-based MOF material;

[0145] The molar ratio of the zinc nitrate hexahydrate, phosphoric acid, oxalic acid, urea, and N,N-dimethylformamide A is 1:4:2:3:80.

[0146] Its infrared data is as follows: 3328 cm -1 : Broad peak of active hydrogen (-OH, -NH-) exists; 1654 cm -1 : -C=O exists;

[0147] 1431 cm -1 : -C-C- exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 381 cm -1 : Zn-O exists; 449 cm -1 : Zn-N exists.

[0148] The preparation method of a degradable MOF amino resin film is the same as that in Specific Example 1.

[0149] Example 6

[0150] A degradable MOF amino resin film, comprising the following raw materials in parts by weight:

[0151] 60 parts of MOF-modified amino resin;

[0152] 30 parts of PVA resin;

[0153] 10 parts of starch

[0154] The above-mentioned MOF-modified amino resin is prepared by the following method:

[0155] Add an aqueous formaldehyde solution of 37 wt%, add potassium hydroxide, adjust the pH to 5, then add urea A and melamine, heat up to 85 °C and react for 1.5 h; add ammonium sulfate to make the pH of the reaction solution 4.5, control the temperature at 85 °C, keep warm until the viscosity reaches 136 cps, add the zinc-based MOF material, continue stirring for 0.8 h, then add urea B, adjust the pH of the reaction solution to 7 with potassium hydroxide, and stop the reaction to obtain the MOF-modified amino resin;

[0156] The dosage ratio of the 37 wt% aqueous formaldehyde solution, urea A, melamine, zinc-based MOF material, and urea B is 100 g: 27 g: 5 g: 10 g: 29 g.

[0157] Its infrared data is as follows: 3366 cm -1 : The broad peak of active hydrogen (-OH, -NH-) exists; 1658 cm -1 : -C=O exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 381 cm -1 : Zn-O exists; 449 cm -1 : Zn-N exists; 1720 cm -1 : 1557 cm -1 、1360 cm -1 、812 cm -1 : The triazine ring exists; the aldehyde group -C=O does not exist.

[0158] The above-mentioned zinc-based MOF material is prepared by the following method:

[0159] Zinc acetate, phosphoric acid, oxalic acid, and urea are dissolved in N,N-dimethylformamide A, and magnetic stirring is continuously carried out at a speed of 300 r / min at room temperature for 15 min until completely dissolved; then it is transferred to a reaction kettle, the reaction kettle is completely sealed and placed in an oven at 120 °C for reaction for 24 h; after the reaction is completed, it is naturally cooled to room temperature, and the obtained product is washed 3 times with N,N-dimethylformamide B and dried at 60 °C for 24 h to obtain the zinc-based MOF material;

[0160] The molar ratio of zinc acetate, phosphoric acid, oxalic acid, urea, and N,N-dimethylformamide A is 1:4:2:3:80.

[0161] Its infrared data is as follows: 3328 cm -1 : The broad peak of active hydrogen (-OH, -NH-) exists; 1654 cm-1 : -C=O exists; 1431 cm -1 : -C-C- exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 381 cm -1 : Zn-O exists; 449 cm -1 : Zn-N exists.

[0162] The preparation method of a degradable MOF amino resin film is the same as that in Specific Example 1.

[0163] Example 7

[0164] A degradable MOF amino resin film, comprising the following raw materials in parts by weight:

[0165] 60 parts of MOF-modified amino resin;

[0166] 30 parts of PVA resin;

[0167] 10 parts of starch.

[0168] The preparation method of the above MOF-modified amino resin is the same as that in Specific Example 1.

[0169] A preparation method of a degradable MOF amino resin film, comprising the following steps:

[0170] (1) Add metaphosphoric acid to the MOF-modified amino resin, stir and mix evenly to obtain an amino resin glue solution for standby;

[0171] The dosage ratio of the MOF-modified amino resin to metaphosphoric acid is 100 g: 3 g;

[0172] (2) Add the PVA resin to deionized water C, stir and dissolve at 50 °C to obtain a PVA solution for standby; add the starch to deionized water D, stir at room temperature for 5 min to obtain a uniform starch dispersion for standby;

[0173] The dosage ratio of the PVA resin to deionized water C is 10 g: 80 g;

[0174] The dosage ratio of the starch to deionized water D is 10 g: 50 g;

[0175] (3) Add the obtained starch dispersion to the PVA solution, stir at 80 °C for 60 min to obtain a uniform PVA / starch blend solution for standby;

[0176] (4) Add the PVA / starch blend solution obtained in step (3) to the amino resin glue solution obtained in step (1), stir and mix at 80 °C for 60 min to obtain a uniform film-forming solution for standby;

[0177] (5) Pour the film-forming solution obtained in step (4) into a flat glass dish and dry it in an oven at 80 °C for 8 h to obtain a degradable MOF amino resin film.

[0178] Example 8

[0179] A degradable MOF amino resin film, comprising the following raw materials in parts by weight:

[0180] 60 parts of MOF-modified amino resin;

[0181] 25 parts of PVA resin;

[0182] 15 parts of starch.

[0183] The preparation method of the above MOF-modified amino resin is the same as that in Example 1.

[0184] The preparation method of a degradable MOF amino resin film is the same as that in Example 1.

[0185] Example 9

[0186] A degradable MOF amino resin film, comprising the following raw materials in parts by weight:

[0187] 60 parts of MOF-modified amino resin;

[0188] 35 parts of PVA resin;

[0189] 5 parts of starch.

[0190] The preparation method of the above MOF-modified amino resin is the same as that in Example 1.

[0191] The preparation method of a degradable MOF amino resin film is the same as that in Example 1.

[0192] The following comparative examples are all compared with Example 1:

[0193] Comparative Example 1

[0194] A degradable amino resin film, comprising the following raw materials in parts by weight:

[0195] 60 parts of amino resin;

[0196] 30 parts of PVA resin;

[0197] 10 parts of starch.

[0198] The above amino resin is prepared by the following method:

[0199] Add 37 wt% aqueous formaldehyde solution, add potassium hydroxide, adjust the pH to 5, then add urea A and melamine. After heating to 85 °C and reacting for 1.5 h, add ammonium sulfate to make the pH of the reaction solution 4.5, control the temperature at 85 °C, and keep the temperature until the viscosity reaches 136 cps. Then add urea B, adjust the pH of the reaction solution to 7 with potassium hydroxide, and stop the reaction to obtain the MOF-modified amino resin.

[0200] The dosage ratio of the 37 wt% aqueous formaldehyde solution, urea A, melamine, and urea B is 100 g: 27 g: 5 g: 29 g.

[0201] Its infrared data is as follows: 3366 cm -1 : There is a broad peak of active hydrogen (-OH, -NH-); 1660 cm -1 : -C=O exists; 1022 cm -1 : -C-O- exists; 1557 cm -1 、1360 cm -1 、812 cm -1 : The triazine ring exists; 1720 cm -1 : The aldehyde group -C=O does not exist.

[0202] The preparation method of a degradable amino resin film is the same as that in Specific Example 1.

[0203] Implementation of Comparative Example 2

[0204] A degradable MOF amino resin film contains the following raw materials in parts by weight:

[0205] 60 parts of MOF-modified amino resin;

[0206] 30 parts of PVA resin;

[0207] 10 parts of starch.

[0208] The preparation method of the above MOF-modified amino resin is the same as that in Specific Example 1, except that the iron-based MOF material is replaced with a zirconium-based MOF material. The preparation method of the zirconium-based MOF material is as follows:

[0209] Zirconium tetrachloride, phosphoric acid, oxalic acid, and urea are dissolved in N,N-dimethylformamide A, and magnetically stirred continuously at a speed of 300 r / min at room temperature for 15 min until completely dissolved. Then transfer to a reaction kettle, seal the reaction kettle completely, and place it in an oven at 65 °C for 3 d. After the reaction is completed, naturally cool to room temperature, wash the obtained product 3 times with N,N-dimethylformamide B, and dry it at 60 °C for 24 h to obtain the zirconium-based MOF material.

[0210] The molar ratio of the zirconium tetrachloride, phosphoric acid, oxalic acid, urea, and N,N-dimethylformamide A is 1:4:2:3:80.

[0211] Its infrared data is as follows: 3328 cm -1 : The broad peak of active hydrogen (-OH, -NH-) exists; 1654 cm -1 : -C=O exists; 1431 cm -1 : -C-C- exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 488 cm -1 : Zr-O exists.

[0212] The preparation method of a degradable MOF amino resin film is the same as that in Specific Example 1.

[0213] Implement Comparative Example 3

[0214] A degradable MOF amino resin film contains the following raw materials in parts by weight:

[0215] 60 parts of MOF-modified amino resin;

[0216] 30 parts of PVA resin;

[0217] 10 parts of starch.

[0218] The preparation method of the above MOF-modified amino resin is the same as that in Specific Example 1, except that oxalic acid is replaced with terephthalic acid.

[0219] The preparation method of a degradable MOF amino resin film is the same as that in Specific Example 1.

[0220] Implement Comparative Example 4

[0221] A degradable MOF amino resin film contains the following raw materials in parts by weight:

[0222] 60 parts of MOF-modified amino resin;

[0223] 30 parts of PVA resin;

[0224] 10 parts of starch.

[0225] The preparation method of the above MOF-modified amino resin is the same as that in Specific Example 1.

[0226] The iron-based MOF material is prepared by the following method:

[0227] Ferric chloride hexahydrate, oxalic acid, and urea are dissolved in deionized water A. After stirring well, it is transferred to a reaction kettle. The reaction kettle is completely sealed and then placed in an oven at 110 °C for reaction for 24 h; after the reaction is completed, it is cooled to room temperature, and the obtained product is washed 3 times with deionized water B and dried at 60 °C for 24 h to obtain an iron-based MOF material;

[0228] The molar ratio of the ferric chloride hexahydrate, oxalic acid, urea, and deionized water A is 1:3:3:80.

[0229] Its infrared data is as follows: 3328 cm -1 : There is a broad peak of active hydrogen (-OH, -NH-); 1654 cm -1 : -C=O exists; 1431 cm -1 : -C-C- exists; 1022 cm -1 : -C-O- exists; 606 cm -1 、432 cm -1 : Fe-O exists; 676 cm -1 : Fe-N exists.

[0230] The preparation method of a degradable MOF amino resin film is the same as that in Specific Example 1.

[0231] Implement Comparative Example 5

[0232] A degradable MOF amino resin film contains the following raw materials in parts by weight:

[0233] 60 parts of MOF-modified amino resin;

[0234] 30 parts of PVA resin;

[0235] 10 parts of starch.

[0236] The preparation method of the above MOF-modified amino resin is the same as that in Specific Example 1.

[0237] The iron-based MOF material is prepared by the following method:

[0238] Ferric chloride hexahydrate, phosphoric acid, and oxalic acid are dissolved in deionized water A. After stirring well, it is transferred to a reaction kettle. The reaction kettle is completely sealed and then placed in an oven at 110 °C for reaction for 24 h; after the reaction is completed, it is cooled to room temperature, and the obtained product is washed 3 times with deionized water B and dried at 60 °C for 24 h to obtain an iron-based MOF material;

[0239] The molar ratio of the ferric chloride hexahydrate, phosphoric acid, oxalic acid, and deionized water A is 1:4:3:80.

[0240] Its infrared data is as follows: 3365 cm -1 : There is a broad peak of active hydrogen (-OH); 1654 cm-1 : -C=O exists; 1431 cm -1 : -C-C- exists; 1022 cm -1 : -C-O- exists; 902 cm -1 : P-O exists; 606 cm -1 and 432 cm -1 : Fe-O exists.

[0241] The preparation method of the degradable MOF amino resin film is the same as that in Specific Example 1.

[0242] Implement Comparative Example 6

[0243] A degradable film comprising the following raw materials in parts by weight:

[0244] 30 parts of PVA resin;

[0245] 10 parts of starch.

[0246] A preparation method of a degradable film, comprising the following steps:

[0247] (1) Add the PVA resin to deionized water C, stir and dissolve at 50 °C to obtain a PVA solution for standby; add the starch to deionized water D, stir at room temperature for 5 min to obtain a uniform starch dispersion for standby;

[0248] The dosage ratio of the PVA resin to deionized water C is 10 g: 80 g;

[0249] The dosage ratio of the starch to deionized water D is 10 g: 50 g;

[0250] (2) Add the obtained starch dispersion to the PVA solution, stir at 80 °C for 60 min to obtain a uniform PVA / starch blend solution for standby;

[0251] (3) Pour the film-forming solution obtained in step (2) into a flat-bottomed glass dish, and dry it in an oven at 80 °C for 8 h to obtain the degradable film.

[0252] Implement Comparative Example 7

[0253] A degradable MOF amino resin film, comprising the following raw materials in parts by weight:

[0254] 60 parts of MOF-modified amino resin;

[0255] 30 parts of PVA resin;

[0256] 10 parts of starch.

[0257] The preparation method of the above MOF-modified amino resin is the same as that in Specific Example 1.

[0258] A preparation method of a degradable MOF amino resin film, comprising the following steps:

[0259] (1) Add PVA resin to deionized water C, stir and dissolve at 50 °C to obtain a PVA solution for standby; add starch to deionized water D, stir at room temperature for 5 min to obtain a uniform starch dispersion for standby;

[0260] The dosage ratio of the PVA resin to deionized water C is 10 g:80 g;

[0261] The dosage ratio of the starch to deionized water D is 10 g:50 g;

[0262] (2) Add the obtained starch dispersion to the PVA solution, stir at 80 °C for 60 min to obtain a uniform PVA / starch blend solution for standby;

[0263] (3) Add the PVA / starch blend solution obtained in step (2) to the MOF-modified amino resin, stir and mix at 80 °C for 60 min to obtain a uniform film-forming solution for standby;

[0264] (4) Pour the film-forming solution obtained in step (3) into a flat-bottomed glass dish, and dry it in an oven at 80 °C for 8 h to obtain the degradable MOF amino resin film.

[0265] Implement comparative example 8

[0266] A degradable MOF amino resin film, comprising the following raw materials in parts by weight:

[0267] 60 parts of MOF-modified amino resin;

[0268] 10 parts of starch.

[0269] The preparation method of the above MOF-modified amino resin is the same as that of specific example 1.

[0270] A preparation method of a degradable MOF amino resin film, comprising the following steps:

[0271] (1) Add ammonium sulfate to the MOF-modified amino resin, stir and mix evenly to obtain an amino resin glue solution for standby;

[0272] The dosage ratio of the MOF-modified amino resin to ammonium sulfate is 100 g:5 g;

[0273] (2) Add starch to deionized water D, stir at room temperature for 5 min to obtain a uniform starch dispersion for standby;

[0274] The dosage ratio of the starch to deionized water D is 10 g:50 g;

[0275] (3) Add the starch solution obtained in step (2) to the amino resin sizing agent obtained in step (1), stir and mix at 80 °C for 60 min to obtain a uniform film-forming solution, and set aside;

[0276] (4) Pour the film-forming solution obtained in step (3) into a flat-bottomed glass dish and dry it in an oven at 80 °C for 8 h to obtain the degradable MOF amino resin film.

[0277] Implement Comparative Example 9

[0278] A degradable MOF amino resin film, comprising the following raw materials in parts by weight:

[0279] 60 parts of MOF-modified amino resin;

[0280] 30 parts of PVA resin.

[0281] The preparation method of the above MOF-modified amino resin is the same as that in Specific Example 1.

[0282] A preparation method of a degradable MOF amino resin film, comprising the following steps:

[0283] (1) Add ammonium sulfate to the MOF-modified amino resin, stir and mix evenly to obtain an amino resin sizing agent, and set aside;

[0284] The dosage ratio of the MOF-modified amino resin to ammonium sulfate is 100 g: 5 g;

[0285] (2) Add the PVA resin to deionized water C, stir and dissolve at 50 °C to obtain a PVA solution, and set aside;

[0286] The dosage ratio of the PVA resin to deionized water C is 10 g: 80 g;

[0287] (3) Add the PVA solution obtained in step (2) to the amino resin sizing agent obtained in step (1), stir and mix at 80 °C for 60 min to obtain a uniform film-forming solution, and set aside;

[0288] (4) Pour the film-forming solution obtained in step (3) into a flat-bottomed glass dish and dry it in an oven at 80 °C for 8 h to obtain the degradable MOF amino resin film.

[0289] The physical properties of the degradable MOF amino resin films of Examples 1-9 and Comparative Examples 1-9 of the present invention were measured respectively, and the results are shown in Table 1.

[0290] Table 1 Physical test properties of each example

[0291]

[0292] First, it can be concluded from Examples 1-9 in Table 1 that the degradable MOF amino resin film of the present invention has excellent degradability, mechanical properties, and gas permeability.

[0293] From Example 1 and Comparative Example 1, it can be observed that the MOF material of the present invention has trace elements for crop growth and can improve the gas permeability and mechanical properties of the film;

[0294] From Example 1 and Comparative Example 2, it can be observed that the MOF material of the present invention has better gas permeability;

[0295] From Example 1 and Comparative Example 3, it can be observed that the MOF material of the present invention has better degradability;

[0296] From Example 1 and Comparative Example 4, it can be observed that the MOF material of the present invention can provide element P for crop production;

[0297] From Example 1 and Comparative Example 5, it can be observed that the MOF material of the present invention has better dispersibility, can improve the mechanical properties of the film, and the amino group has a positive effect on the permeation of CO2 in terms of gas permeability;

[0298] From Example 1 and Comparative Examples 6-9, it can be observed that the degradable MOF amino resin film of the present invention combines the strength of amino resin, the gas barrier property of PVA resin, and the rapid degradability of starch, and has excellent mechanical properties, a short degradation period, and gas selective permeability.

[0299] In summary, a degradable MOF amino resin film provided by the present invention, through molecular design, has the advantage of being completely degradable. The degradation process is a slow-release process of fertilizer efficiency, has abundant elements required for crop growth, and excellent gas selective permeability.

[0300] The test methods are as follows:

[0301] (1) Tensile strength: Tested according to the method described in GB / T 1040-2006.

[0302] (2) Gas permeability: The purpose of the agricultural film is to reduce O2 in crops and increase CO2. The gas permeability was analyzed by the variable volume / constant pressure method to measure the gas transport characteristics at 25 °C and a pressure of 6 bar. The permeabilities of CO2 and O2 gases were measured. The purity of the gases used was greater than 99.5%. The gas permeability of the prepared film was calculated by the following formula:

[0303] P i =[l / (AΔP)](dV i / dt)

[0304] P iIt represents the air permeability of penetrant i, ΔP is the transmembrane pressure drop (cm Hg), and A and l are the effective membrane area (cm 2 ) and the thickness of the membrane, respectively. dt is the permeation rate (cm 3 (STP) / s).

[0305] (3) Degradation rate in soil: Place the degradable MOF amino resin membrane outdoors and completely cover it with soil. Regularly observe the state of the membrane until it is completely degraded.

[0306] (4) Nutrient release rate in soil culture: Accurately weigh the degradable MOF amino resin membrane, seal it after putting it into a nylon mesh bag with a pore size of 2.0 mm. Weigh 200 g of air-dried paddy soil with a pore size of 0.6 mm and put it into a 250 mL plastic bottle. Bury the nylon mesh bag containing the degradable MOF amino resin membrane into the soil to ensure that the membrane is in full contact with the soil in the soil. Calculate according to the maximum water holding capacity of 33.3 g per 100 g of soil, adjust the relative soil water content to 60%, and then seal it with plastic wrap. Place all plastic bottles in an incubator at 25°C for cultivation, weigh the plastic bottles once at regular intervals, and replenish the lost water. Take samples on the 40th day and 90th day respectively, collect soil samples, take out 5 bottles each time, and calculate the average value. The contents of available iron, available phosphorus, and available sulfur in the soil are determined by an iCAP7000 ICP-OES spectrometer (Thermo Fisher Scientific, USA); the mineral nitrogen in the soil is determined by a SmartChem200 automatic analyzer (Alliance, France). Statistically calculate the cumulative release rate of each nutrient.

[0307] Enlightened by the above ideal embodiments according to the present invention, through the above description, relevant staff can completely make various changes and modifications without departing from the technical idea of this invention. The technical scope of this invention is not limited to the content in the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A degradable MOF amino resin film, characterized in that, It consists of the following raw materials by weight parts: 40 - 70 parts of MOF-modified amino resin; 20 - 35 parts of PVA resin; 5 - 30 parts of starch; The dosage of the MOF-modified amino resin is based on solid content; The MOF-modified amino resin is prepared by the following method: Add formaldehyde solution, add potassium hydroxide, adjust the pH to 4.5 - 5.5, then add urea A and melamine, heat up to 85 - 90 °C and react for 1 - 1.5 h; add acid to make the pH of the reaction solution 4.0 - 5.0, control the temperature at 80 - 90 °C, keep warm until the viscosity reaches 100 - 150 cps, add MOF material, continue stirring for 0.5 - 1 h, then add urea B, adjust the pH of the reaction solution to 6.5 - 7.5 with potassium hydroxide, and stop the reaction to obtain the MOF-modified amino resin; The dosage ratio of the formaldehyde solution, urea A, melamine, MOF material, and urea B is 100 g: 24 - 30 g: 5 g: 5 - 20 g: 25 - 31 g; The formaldehyde solution is a 37 wt% aqueous formaldehyde solution; The MOF material is an iron-based MOF material or a zinc-based MOF material; The zinc-based MOF material is prepared by the following method: Zinc salt, phosphoric acid, oxalic acid, and urea are dissolved in N,N-dimethylformamide A, and magnetically stirred at a speed of 300 r / min at room temperature for 15 min until completely dissolved; then transferred to a reaction kettle, the reaction kettle is sealed completely and placed in an oven at 120 °C for 24 h; after the reaction is completed, it is naturally cooled to room temperature, and the obtained product is washed 3 times with N,N-dimethylformamide B and dried at 60 °C for 24 h to obtain the zinc-based MOF material; The molar ratio of the zinc salt, phosphoric acid, oxalic acid, urea, and N,N-dimethylformamide A is 1:4:2:3:80; Among them, the preparation method of the degradable MOF amino resin film includes the following steps: (1) Add an acidic curing agent to the MOF-modified amino resin, stir and mix evenly to obtain an amino resin glue solution for standby; the dosage ratio of the MOF-modified amino resin to the acidic curing agent is 100 g: 3 - 5 g; (2) Add the PVA resin to deionized water C, stir and dissolve at 50 °C to obtain a PVA solution for standby; add the starch to deionized water D, stir at room temperature for 5 min to obtain a uniform starch dispersion for standby; The dosage ratio of the PVA resin to deionized water C is 10 g: 80 g; The dosage ratio of the starch to deionized water D is 10 g: 50 g; (3) Add the obtained starch dispersion to the PVA solution, stir at 80 °C for 60 min to obtain a uniform PVA / starch blend solution for standby; (4) Add the PVA / starch blend solution obtained in step (3) to the amino resin glue solution obtained in step (1), stir and mix at 80 °C for 60 min to obtain a uniform film-forming solution for standby; (5) Pour the film-forming solution obtained in step (4) into a flat glass dish, and dry it in an oven at 60 - 80 °C for 8 - 12 h to obtain the degradable MOF amino resin film; The iron-based MOF material is prepared by the following method: The iron salt, phosphoric acid, oxalic acid, and urea are dissolved in deionized water A. After stirring well, it is transferred to a reaction kettle. The reaction kettle is completely sealed and placed in an oven at 100-110°C for reaction for 24-30 h; after the reaction is completed, it is cooled to room temperature. The obtained product is washed 3 times with deionized water B and dried at 60°C for 24 h to obtain the iron-based MOF material; The molar ratio of the iron salt, phosphoric acid, oxalic acid, urea, and deionized water A is 1:4:3:3:80; The acidic curing agent is ammonium sulfate or metaphosphoric acid.

2. The preparation method of a degradable MOF amino resin film according to claim 1, wherein: The acid is ammonium sulfate.

3. The preparation method of a degradable MOF amino resin film according to claim 1, characterized in that: The iron salt is ferric chloride hexahydrate or ferric nitrate nonahydrate.

4. The preparation method of a degradable MOF amino resin film according to claim 1, characterized in that: The zinc salt is zinc nitrate hexahydrate or zinc acetate.

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